Conventionally, p-NiO/n-Si (p-n) heterojunction photodiodes (HPDs) exhibit a larger visible response than the ultraviolet response due to the thick Si substrate; hence, it is used as a broadband photodetector with a poor ultraviolet (UV)-to-visible rejection ratio. Herein, an intrinsic NiO (i-NiO) layer is inserted between the p-NiO and the n-Si substrate to fabricate p-NiO/i-NiO/n-Si (p-i-n) HPDs, significantly suppressing leakage current and visible response. Compared with the conventional p-n HPDs, the insertion of the i-NiO layer significantly reduces leakage current by approximately 241 times and enhances the rectification ratio from 13.8 to 3228 for the p-n and p-i-n HPDs. The insertion of an i-NiO layer not only increases the UV-response but also suppresses the visible response. These issues enhance the UV-to-visible rejection ratio from 72.2 in p-n HPDs to 915.3 in p-i-n HPDs. The p-NiO reveals a poorer crystalline structure than the i-NiO film because the Ag dopants accumulate at the grain boundary and inhibit crystalline growth. The Ag diffusion in the Si substrate causes defect states within the Si bandgap, whereas it is retarded by the i-NiO layer in the p-i-n HPDs. The poor crystallinity in the p-NiO and defect states within the Si bandgap contributes to a high leakage current and visible response in p-n HPDs. The p-i-n HPDs demonstrate a higher UV-response due to absorption by the i-NiO layer. Because visible light cannot be absorbed by the i-NiO layer, visible response is suppressed in p-i-n HPDs.